Vat dye assistants and method of using



Patented Mar. 16, 1937 UNITED STATES PATENT OFFICE Jean G. Kern,

Hamburg,

N. Y., assignor to National Aniline and Chemical Company, Inc., New York, N. Y., a corporation of New York No Drawing. Application May 1, 1934, Serial No. 723,332

10 Claim.

This invention relates to the art of dyes and dyeing. It relates more particularly to a new class of vat assistants and to vat dye liquors or pastes and vat dyeing processes, especially printing pastes and printing processes comprising or employing such assistants, by means of which dyeings or prints of excellent fastness, depth, and brilliance may be obtained.

As is well known, vat' dyes are water-insoluble solids and when used to dye textile fibers, they are ordinarily converted to a water-soluble (leuco) form (as by treatment with a reducing agent such as sodium hydrosulfite or formaldehyde sulfoxylate and potassium carbonate); in

this form they are taken up by the fibers and are then rendered insoluble by an oxidizing or fixing treatment.

The printing process for dyeing textile fabrics generally involves applying a so-called printing paste to the fabric in the form of a design (for example by means of a screen, a stencil, or an engraved roll) and subsequently subjecting the printed fabric to further treatment to fix the dye upon the fibers.

Usually vat dye printing pastes contain, in addition to the vat dye, potential reducing agents,- substances which in themselves do not reduce the vat dye under the conditions of the printing operation but which upon application of heat with or without steam are capable of reducing the vat dye to the soluble leuco form. A mixture of sodium formaldehyde sulfoxylate and potassium carbonate is usually used as this reducing agent. The printing paste also ordinarily contains substances which promote the reduction of the dye or the absorption of the reduced compound by textile fibers, and suitable gums or thickeners. In some cases, as in printing with dlflicultly reducible vat dyes, the vat dye in the o printing paste is subjected to a preliminary reduction before applying the printing paste to the fabric.

The heat treatment above referred to, ordinarily designated "aging, usually comprises subjecting the printed fabric to a short treatment with wet (saturated) steam while excluding oxygen, e. g., air, whereby the vat dye is reduced to the leuco form or its reduction is rendered more complete. This causes the dye to be absorbed more completely by the fiber.

After application of the printing paste to the fabric, and aging when this is employed, the fabric is subjected to an oxidlzingtreatment by 55 passing it through an atmosphere containing an oxidizing agent, e. g. air, or through a bath containing an oxidizing agent, e. g. a bath containing acetic acid and sodium dichromate. This oxidizing treatment converts the reduced vat dye compound back to the insoluble form upon the 5 fiber. The fabric bearing the oxidized print is then washed, soaped, and rinsed, or otherwise suitably finished.

Vat dyes, when printed on textile fabrics with the aid of alkali-metal hydroxides, carbonates, or 10 bicarbonates, frequently fail to yield full color value. This may be attributed to improper fixation of the dye on the fibers because of varying aging conditions or varying physical condition of the vat dye printing paste. 15

In accordance with the present invention, I have found that certain aryl ketones, though they themselves have no tinctorial power, nevertheless are excellent assistants or adjuvants for the application of vat dyestuffs in dyeing proc- 20 esses involving vat dyes. They are especially efiective for assisting the conversion of vat dyes to their leuco form or for causing more complete conversion to this form, and hence they may be employed to advantage in all processes involving such a step. I have found, moreover, that vat dye printing pastes containing such compounds as assistants yield fast prints having excellent penetration, strength, and brilliance.

The ketones which I employ may be represented by the formula wherein R represents an aryl radical of the 35 benzene or naphthalene series, especially the former, and R represents either a carboxyl group or a low-molecular alkyl, aryl, or aralkyl group, and wherein either R or R, or both, contain a group conferring solubility in water or alkaline solutions, for example an SO3Me, --COOMe, OMe, or SMe group, where Me represents hydrogen, a metal, an ammonium group, or an alkylor hydroxy-alkyl-substituted ammonium group (thus forming an amine salt). In view of their high water-solubility, I prefer to employ those ketones, the water-solubility conferring group of which is COOMe or SOzMe, the latter especially. It will be understood that R and R are separate radicals joined only through a single C=O group and that either or both may contain further substituents. e. g. alkyl-, oxy-, mercapto-, halogen-, sulfonate-, carboxy-, or amino-groups. As an example of amine salts may be mentioned the amine salt of 2-benzoyibenzoic acid and diethanolamine.

5 e. 8. those of Na and K:

G O H D C 2- benzoyi-benzoic acid OaBOH benzophenone-2-sultonic acid 2- i-methyl-benzoyl -bemoic acid benzophenoneZ-carboxy4'-sultonic acid 2- (3-amino-4-chior-benzoyl -benzoic acid nosoa-O-c-em acetophenonesultonic acid benzoyl-acetic acid 2- (4-chlor-benzoyl -benzoic acid 2- [l-hydroxy-naphthoyl- 2 ]-benzoic acid O-i-COOH bensoyi-tormic acid GK-COOH 2-amlno-bensoyi-tcrmic acid (iatlnic acid) OH Oman Z-hydroxy-benzoyi-tormic acid SH Oil-000E 2-mercapto-benzoyi-tormic acid 0 pl-COOK l-naphthoyl-tormic acid OH OH 2,3,4'trihydroxybenzophenone H0 0 C O O O H 3-benzoyl-phtha1ic acid OiSOH 2,4-dihydroxybenzophenone-2'-sulfonic-acid 2- (alphanaphthoyl -i enzoic acid on coon and coon

2-phenylacetyi-bensoic acid The vat dye pastes of the present invention are suitable for application to the same types of fibers as ordinary vat printing pastes, for exampie, natural celiuloses (e. g. cotton), regenerated celluloses, cellulose esters and ether-s (e. 3., the cellulose acetates and nitrates), and natural silk, as well as mixed goods manuiactured from such fibers.

The printing pastes 01' this invention may be prepared in the usual manner with vat dyes of all types including those derived from anthraquinones, indophenols, various indigoid, thioindigoid and indirubin compounds, etc; for example, indanthrones, pyranthrones, flavanthnones, dibenzanthrones, isodihenzanthrones, perylene quinones, anthanthrones, dibenzpyrene quinones, anthrimidocarbazols, naphthacridones, indigo. thioindigo, indirubin, etc. including" derivatives thereof. such as their halogen, nitro, suli'ur. and

-' duced tormi The tion.

-thioindigo series. .'however-.-.- flh ffollowing dyes C. I. "Vat Orange?- s 1217 Tetrabrom Indigo 1184 Indanthrene Blue GCD'. 1113 Indanthren'e Dark Blue B014 1099 Fiavanthron 1118 Pyranthrone- Y 1096 Indanthrene Golden Orange R.--.-..c--...-- 1097 Indanthrene Scarlet G 1 1098 "Carbanthrene Blue Green FFB 1173 I Carbanthrene Violet 2R 1104 --"-Carbanthrene RedViolet ZRNIL; 1181 Carbanthrene Brilliant Green 1101 Vat'R/ed Violet RH 1212' Val; Scarlet G s i228 vat Rink FF n. 5.2. 892,897)

.YatYioletE" j f 1222 Brilliantlindigo B 1183 Brilliant, digo 1 (.i- 1189 "with whichgthe invention man be empl y to advantage are set,10rth;toexemp liiy the general algplicability. or the invention;

DinaphthyI-thioindIgOL,

The dye pastes or rinting pastes'oi the present invention,=oi course,. may contain the usnal additions, among which maybe mentioned alkaline reagents, e. g. alkali=metal hydroxides, carbonates. or bicarbonates. reducing agents, a. g.. alkalimetal-hydrosuliites ior alkall-metal-formaldehyde-sulioxylates, and suitable thickening agents,

, 'e. g.- starch, dextrin, mucilage. glue, British gum.

contain well as the i arable, and gumtragacanth, They may =aryl ketones herein 'described-assistants, such asrglycerlne, alcohols.

a by weight.

ethersror amines, orhydrotrbplc reagents (as defined in my copending application Serial No. 673,03lpflled May 26, 1933) e: application and development or printing pastes ot-thepresent invention maybe eiiected in the c ary manner for applying vat dye printing pastes.

' The following examples'will serve to illustrate the invention; Proportions are expressed as parts part of sodium z-benaoyl-benspate is dissolved in 19 parts of a dyestuil' paste containing-115% VatOrange R [the remainder "of the being mainly water,-which may contain m damen a dispersing agent '(leukanol) and lorglycrlnel'fi The resultant paste is inti-- mately mixed with to parts of'a reducing paste whichis prepared by mixing 52 parts of a starch (British gum) tragacanth thickening paste [e. g. 2 parts cornstarch. 10 parts British gum, 2 parts 5% tragacanth (solution), and 38 parts water]. 15 parts potassium carbonate, 16 parts water. 12 parts sodium formaldehyde-sulfoxylate, and 5 a parts glycerine.

iprints reducing paste described is well-fixed to the fiber, to 20%stmnger and more brilliant than obtained by the same procedure, omitting the sodium z-benzoyl-benroate from the printing paste.

Example z.1partoithedisodlumsalto1benzophenone-z-carboiw-f-sulfonate is dissolved in 19 parts of a dyestuii paste containing 20% tetrabromindigo (the remainder oi the paste being inert material). mixed with parts oi a reducing paste prepared as described in Example 1. This printing paste, upon application to and development upon a textile fabric, for example a cotton fabric, yields prints of superior brilliance and increased strength over ,those obtained with a printing paste lacking the disodium benzophenone-z-carboxy-4'-sulionate but otherwise the same.

Example 3.-200 parts of a dyestuii paste containing 16% Indanthrene Blue GCD (C. I. 1113) are intimatelymixed with 50 parts of the disodium salt of benzophenone-z-carboxy-f-sulionate. 3 parts sodium isopr pylnaphthalene-sulionate, and parts of soluble dextrin. The homogeneous mixture thus obtained is dried in vacuum and ground to the desired fineness. The resultant powder can be used in the same manner as ordinary vat dyestuii powders for the production of prints on textiles and, when so applied, yields prints 0! high brilliance and strength.

Example 4.10 parts mixed with parts of ducing paste described in Example 1. The paste thus formed may be printed on cotton or other textile fabric, aged. and developed by the method of Example 1 yielding a fuller and stronger print than obtainable with omission of the sodium isatinate.

It is not necessary that the ketone be introduced as such into the paste but it may be formed from another compound or other compounds under the conditions of application and it will be understood that the invention includes such formation of the ketone within its scope. Thus, isatin, which when heated in alkaline media forms a salt of 2-amlno-benzoyl-formic acid (is atinic acid), may be employed instead of the sodium isatin'ate of Example 4, as in the following'example.

Emmple 5.'1 part of isatin is mixed with 19 parts of an aqueous 15% 'Vat Pink FF paste. The mixture is evaporated down to l9.parts. The mixture is then mixed with 76 parts 01 the in Example 1. The paste thus formed may be printed on cotton. aged, and developed by the method of Example 1. A fuller and stronger print is obtained than when the isatin is omitted. Since vat dye prints are aged by application of heat to the alkaline paste isatin present is converted to an alkali-metal isatinate. Accordingly either isatin or'isatinlc acid or a soluble isatinate may be used with substantially the same results.

It will be understood that the vat dy: powder: obtained according to the foregoing example: and/or other similarly obtained vat dye preparations, either in a paste or powder form. and con talning the aryl-ketonic bodies as disclosed it this invention. may also be used for the tintin and dyeing of textile fibers by the methods re ferrcd to as dyeing operations. including as sue] the pad-iigg dyeing method, package dyeing andisordinari1y The resultant paste is intimately 1 of sodium isatinate' are I 'dyestufl. and a non-foaming -1. In the preparation 01 dyed textile fibers, the step which comprises bringing theflbers into contact with a vat dyestuii and a non-roaming aryl ketone having the general iormula wherein it represents an aryl radical oi the bensene or naphthalene series and It represents a carboxyl group or a low molecular alkyl, aryl, or 16 arallwl group, and which ketone contains a group conferring solubility in water or alkaline'solution. 2. In the preparation of dyed textile fibers, the step which comprises subjecting a vat dyestuii in contact with the fibers to the action of a reduc- 90 ins agent in the presence of a non-foaming ary ketone having the general formula -R-;-COR whereinR tsanarylradicalottheben 25 sene .or naphthaleneseries and R represents a 'carboxyl group or a low molecularalkyl, aryl, or aralkyl group, and which ketone contains a group conferring solubility in water or alkaline solution. 8. In the printing of a textile fabric, the step which-comprises applying to the fabric a printing paste comprising a vat 'dyestuii and a nonfoaming aryl ketone having the general formula R-CO-R' 35 wherein Rrepresents an aryl radical of the henzene or naphthalene series and R represents a carboni 0 .1 alow molecular alkyl. aryl, or 'arailwl group. and which ketone contains a group 'coni'erring solubility in water or alkaline solution.

4.-The'method ot producinga printed .textile fabric, which comprises printing upon the iabrlc R represents at the ben-ii' jsene or naphthalene series and R represents a ,carboxyl group or a low molecular alkyl. aryl. or

5Q arallryl 'group, and which ketone comprises .a

--CO0Me or '-BO:Me group, He representing 'an alkaii-metai,.and subsequently aging and de velopingtheprint. 5.A d'yestuflcompositioncomprising a vat aryl ketone having 1 the general iormula R-GO-It' arailwl smear-em fhi zene o naphthalene series a VI- 17. 2: a carbo yl ora-i am wl r'zslml L Q? 6. A18? a dye-stuil. a n clli ekmducipsasnt. vmili assistant. dispersed in an alkaline 'n'idium. said assistant comprisingsa nonioan ins wherein t-R i-rem ssh ma A aryl ketone thegeneral gorlriifls I v wherein R z'ene or naphthalene series more a carboiwl group'ore low moiecular alkyljarylg or.

araliwl group. and whichiketone a -GOOMe or -spor group. Me, representing an alkali-metal. I I a I. A vat dye powd compri i a vat dyestuir and a solid nonfoaming aryl' ketonehaving the generaiiormula 'l, v 1

7 x wherein R represents an aryl radical of the. henzene or naphthalene series and R represents a carbonyl group or a low molecular allwl. aryl, or arallwl group and which ketone contains a group conien'ing solubility in water or alkaline solution. 8. In the application of a vat dyestuil. to textile nbers, the step which comprises subjecting fibers with the vat dyestuit thereon to-an treatment in the presence of a; non-foaming aryi ketone having the general formula wherein R an aryl radical oi the ben- .aene or naphthalene series and R represents a f -carboxyl group ora low molecular alkyl, aryl, br aralkyl group. and which ketone '-comprises a an alkali-metal. 4

-CO0Me or -SO;Me

1 9. In the application of. a vat to textile fibers, the step which comprises bringing the fibers into contact with thefvat dyesmii and an 8.471 ketone having the formula V ECO-R wherein R and R represent aryl radicals of the benzene series, and which ketone comprises an ---8O:Me group whereinMe represents hydrogen or a metal.

10. In the preparation of dyed textile .fibers, the step which comprises br n n the fibers into contact with a vat dyestui'i and a diaryl ketone containing} group conferring solubility in water or alkaline solution.

JEAN G. KERN. 

